Use of metal complex compounds as oxidation catalysts

ABSTRACT

The use of metal complexes of compounds of formula I  
                 
wherein the general symbols are as defined in claim 1, as oxidation catalysts.

The present invention relates to the use of metal complex compounds asoxidation catalysts. The present invention relates also to formulationscomprising such metal complex compounds, to novel metal complexcompounds and to a method of catalysing oxidations, wherein at least onecomplex compound according to the invention is added to the oxidisingagent.

The metal complex compounds are used especially for improving the actionof peroxides, for example in the treatment of textile material, withoutat the same time causing any appreciable damage to fibres and dyeings.

Peroxide-containing bleaching compositions have been used in washing andcleaning processes for some time. They have an excellent action at aliquor temperature of 90° C. and above, but their performance noticeablydecreases with lower temperatures. It is known that various transitionmetal ions, added in the form of suitable salts, or coordinationcompounds containing such cations, catalyse the decomposition of H₂O₂.In that way it is possible to increase the bleaching action of H₂O₂, orof precursors that release H₂O₂, or of other peroxo compounds, thebleaching action of which is unsatisfactory at lower temperatures.Particularly significant for practical purposes are those combinationsof transition metal ions and ligands the peroxide activation of which ismanifested in an increased tendency towards oxidation in respect ofsubstrates and not only in a catalase-like disproportionation. Thelatter activation, which tends rather to be undesirable in the presentcase, could impair the bleaching effects of H₂O₂ and its derivativeswhich are insufficient at low temperatures.

In respect of H₂O₂ activation having effective bleaching action,mononuclear and polynuclear variants of manganese complexes with variousligands, especially with 1,4,7-trimethyl-1,4,7-triazacyclononane andoptionally oxygen-containing bridge ligands, are currently regarded asbeing especially effective. The catalysts disclosed e.g. inWO-A-01/64697 have adequate stability under practical conditions and,with Mn^(n+), contain an ecologically acceptable metal cation, but theiruse is unfortunately associated with considerable damage to dyes andfibres.

The aim of the present invention was, therefore, to provide improvedmetal complex catalysts for oxidation processes which fulfil the abovedemands and, especially, improve the action of peroxy compounds in anextremely wide range of fields of use without giving rise to anyappreciable damage.

The invention accordingly relates to the use of metal complex compoundsof formula I

wherein

-   X is oxygen or-   R₁ and R₂ each independently of the other are halogen, hydroxy,    cyano, nitro,    —SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted    C₁-C₈alkoxy; chloro-substituted C₁-C₈alkyl; chloro-substituted    C₁-C₈alkoxy; C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino,    C₁-C₈acylamino, di(C₁-C₄alkyl)amino,    di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl, R₃ is    hydrogen, C₁-C₁₂alkyl, phenyl or-   R₄ is —OR₁₀, —NH₂, —NHR₁₁,-   R₅ is —OR₁₀, C₁-C₈alkyl or —NH₂,-   R₆ is hydrogen, C₁-C₈alkyl or C₇-C₉phenylalkyl,-   R₇ is hydrogen, C₁-C₈alkyl or C₇-C₉phenylalkyl,-   R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene,-   R₉ is halogen, hydroxy, cyano, nitro,    —SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted    C₁-C₈alkoxy; chloro-substituted C₁-C₈alkyl; chloro-substituted    C₁-C₈alkoxy; C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino,    C₁-C₈acylamino, di(C₁-C₄alkyl)amino,    di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl,-   R₁₀ is hydrogen, sodium or potassium,-   R₁₁, and R₁₂ each independently of the other are C₁-C₈alkyl,-   Y⁻ is a monovalent anion,-   m is 1 or 2, and-   n is 0, 1, 2 or 3;    as oxidation catalysts.

Halogen is, for example, fluorine, chlorine, bromine or iodine. Chlorineis preferred.

Fluoro-substituted C₁-C₈alkyl is a branched or unbranched radical, forexample fluoromethyl, difluoromethyl, trifluoromethyl orpentafluoroethyl. Trifluoromethyl is preferred.

Fluoro-substituted C₁-C₈alkoxy is a branched or unbranched radical, forexample fluoromethoxy, difluoromethoxy, trifluoromethoxy orpentafluoroethoxy. Trifluoromethoxy is preferred.

Chloro-substituted C₁-C₈alkyl is a branched or unbranched radical, forexample chloromethyl, dichloromethyl, trichloromethyl orpentachloroethyl. Chloromethyl and trichloromethyl are preferred.

Chloro-substituted C₁-C₈alkoxy is a branched or unbranched radical, forexample chloromethoxy, dichloromethoxy, trichloromethoxy orpentachloroethoxy. Trichloromethoxy is preferred.

C₇-C₉-Phenylalkoxy is, for example, benzyloxy, α-methylbenzyloxy orα,α-dimethylbenzyloxy. Benzyloxy is preferred.

Alkylamino having up to 8 carbon atoms is a branched or unbranchedradical, for example methylamino, ethylamino, propylamino,isopropylamino, n-butylamino, isobutylamino or tertbutylamino.

Acylamino having up to 8 carbon atoms is a branched or unbranchedradical, for example formylamino, acetylamino, propionylamino,butanoylamino, pentanoylamino, benzoylamino or octanoylamino.Acetylamino is preferred.

Di(C₁-C₄alkyl)amino also means that the two radicals each independentlyof the other are branched or unbranched, for example dimethylamino,methylethylamino, diethylamino, methyl-n-propylamino,methyl-isopropylamino, methyl-n-butylamino, methyl-isobutylamino,ethyl-isopropylamino, ethyl-n-butylamino, ethyl-isobutylamino,ethyl-tert-butylamino, di-isopropylamino, isopropyl-n-butylamino,isopropyl-isobutylamino, di-n-butylamino or di-isobutylamino.

Di(C₁-C₄acyl)amino also means that the two radicals each independentlyof the other are branched or unbranched, for example diacetylamino,acetyl-propionylamino, dipropionylamino or dibutanoylamino.

Alkyl having up to 12 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl or dodecyl.

Alkoxy having up to 8 carbon atoms is a branched or unbranched radical,for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentyloxy, isopentyloxy, hexyloxy, heptyloxy or octyloxy.

Alkanoyl having up to 8 carbon atoms is a branched or unbranchedradical, for example formyl, acetyl, propionyl, butanoyl, pentanoyl,hexanoyl, heptanoyl or octanoyl.

Unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene is a branched orunbranched radical, for example methylene, ethylene, propylene,trimethylene, tetramethylene, pentamethylene, hexamethylene,heptamethylene, octamethylene, decamethylene or dodecamethylene.C₂-C₈Alkylene, especially C₃-C₅alkylene, is preferred.

Metals suitable for the formation of metal complexes of compounds offormula I are, for example, iron, especially in oxidation states I toIV; manganese, especially in oxidation states II-V; titanium, especiallyin oxidation states III and IV; cobalt, especially in oxidation states Ito III; nickel, especially in oxidation states I to III; and alsocopper, especially in oxidation states I to III.

Of interest is the use of metal complexes of compounds of formula Iwherein

-   X is oxygen or

R₁ and R₂ each independently of the other are chlorine, bromine,hydroxy, cyano, nitro,

—SO₂R₅, trifluoromethyl, trifluoromethoxy; chloromethyl,trichloromethyl, trichloromethoxy, benzyloxy, amino, C₁-C₄alkylamino,C₁-C₄acylamino, di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₄alkyl, C₁-C₄alkoxy or C₂-C₄alkanoyl,

-   R₃ is hydrogen, C₁-C₈alkyl, phenyl or-   R₄ is —OR₁₀, —NH₂, —NHR₁₁,-   R₅ is —OR₁₀, C₁-C₄alkyl or —NH₂,-   R₆ is hydrogen, C₁-C₄alkyl or benzyl,-   R₇ is hydrogen, C₁-C₄alkyl or benzyl,-   R₈ is C₂-C₈alkylene,-   R₉ is fluorine, chlorine, bromine, hydroxy, cyano, nitro,    —SO₂R₅, trifluoromethyl; trifluoromethoxy; chloromethyl,    trichloromethyl, trichloromethoxy, benzyloxy, amino,-   C₁-C₄alkylamino, C₁-C₄acylamino, di(C₁-C₄alkyl)amino,    di(C₁-C₄acyl)amino, C₁-C₄alkyl, C₁-C₄alkoxy or C₂-C₄alkanoyl,-   R₁₀ is hydrogen, sodium or potassium,-   R₁₁, and R₁₂ each independently of the other are C₁-C₄alkyl,-   Y⁻ is halide, nitrate or carboxylate,-   m is 1 or 2, and-   n is 0, 1 or 2.

Of special interest is the use of metal complexes of compounds offormula I wherein

-   X is oxygen or-   R₁ and R₂ each independently of the other are chlorine, hydroxy,    cyano,    —SO₂R₅, C₁-C₄acylamino, di(C₁-C₄alkyl)amino,    di(C₁-C₄acyl)amino, C₁-C₄alkyl, chloromethyl, methoxy or    C₂-C₄alkanoyl,-   R₃ is hydrogen, C₁-C₈alkyl, phenyl or-   R₄ is —OR₁₀, —NH₂, —NHR₁₁ or-   R₅ is —OR₁₀, methyl or —NH₂,-   R₆ and R₇ each independently of the other are hydrogen, C₁-C₄alkyl    or benzyl,-   R₉ is chlorine, hydroxy, cyano, nitro,    —SO₂R₅ or methoxy,-   R₁₀ is hydrogen, sodium or potassium,-   R₁₁, and R₁₂ each independently of the other are C₁-C₄alkyl,-   Y⁻ is chloride or carboxylate,-   m is 1, and-   n is 0 or 1.

Special preference is given to the use of metal complexes of compoundsof formula I wherein

the metal is iron or manganese,

-   X is oxygen or    and-   R₃ is hydrogen, C₁-C₄alkyl, phenyl or-   R₄ and R₅ are —OR₁₀,-   R₉ is    or —SO₂R₅,-   R₁₀ is hydrogen,-   m is 1, and-   n is 0.

Ligands of formula I are known in the literature or can be obtainedanalogously to known processes.

The preparation of the compounds of formula I is preferably carried outby reaction of a compound of formula II with a compound of formula III

wherein R₁, R₂, n and X are as defined above.

The reaction is preferably carried out in a solvent, for exampleethanol, by boiling for several hours under reflux.

Some of the metal complexes of compounds of formula I according to theinvention are known and can be obtained analogously to known processes.They are obtained in a manner known per se by reacting at least onecompound of formula I in the desired molar ratio with a metal compound,especially a metal salt, such as the chloride, to form the correspondingmetal complex. The reaction is carried out, for example, in a solvent,such as water or a lower alcohol, such as ethanol, at a temperature of,for example, from 10 to 60° C., especially at room temperature.

The present invention relates also to the novel metal complexes ofcompounds of formula I

wherein

-   X is oxygen or-   R₁ and R₂ each independently of the other are halogen, hydroxy,    cyano, nitro,    —SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted    C₁-C₈alkoxy; chloro-substituted C₁-C₈alkyl; chloro-substituted    C₁-C₈alkoxy; C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino,    C₁-C₈acylamino, di(C₁-C₄alkyl)amino,    di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl,-   R₃ is hydrogen, C₁-C₁₂alkyl, phenyl or-   R₄ is —OR₁₀, —NH₂, —NHR₁₁,-   R₅ is —OR₁₀, C₁-C₈alkyl or —NH₂,-   R₆ is hydrogen, C₁-C₈alkyl or C₇-C₉phenylalkyl,-   R₇ is hydrogen, C₁-C₈alkyl or C₇-C₉phenylalkyl,-   R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene,-   R₉ is halogen, hydroxy, cyano, nitro,    —SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted    C₁-C₈alkoxy; chloro-substituted C₁-C₈alkyl; chloro-substituted    C₁-C₈alkoxy; C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino,    C₁-C₈acylamino, di(C₁-C₄alkyl)amino,    di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl,-   R₁₀ is hydrogen, sodium or potassium,-   R₁₁ and R₁₂ each independently of the other are C₁-C₈alkyl,-   Y⁻ is a monovalent anion,-   m is 1 or 2, and-   n is 0, 1, 2 or 3.

Of special interest are the novel metal complexes of compounds offormula I wherein the metal is iron or manganese,

-   X is oxygen or-   R₃ is hydrogen, C₁-C₄alkyl, phenyl or    -   R₄ and R₅ are —OR₁₀,-   R₉ is    or —SO₂R₅,-   R₁₀ is hydrogen,-   m is 1, and-   n is 0.

The metal complexes of compounds of formula I are preferably used inwashing, cleaning, disinfecting or bleaching compositions.

The metal complexes of compounds of formula I are preferably usedtogether with peroxy compounds for the bleaching of spots or stains ontextile material or for the prevention of redeposition of migrating dyesin the context of a washing process, or for the cleaning of hardsurfaces, for example table- and kitchen-ware, glass, wall tiles orfloor tiles. It is preferred to use aqueous formulations of the metalcomplexes of compounds of formula I for this purpose.

Of special interest is the use of metal complexes of compounds offormula I for the removal of stains caused by the action of molds (moldstains); use in washing and cleaning solutions having an antibacterialaction; or as pretreatment agents for bleaching textiles.

Also of interest is the use of metal complexes of compounds of formula Ias catalysts for selective oxidations in the context of organicsynthesis.

A further use relates to the use of metal complexes of compounds offormula I as catalysts for reactions with peroxy compounds for bleachingin the context of paper-making. This relates especially to the bleachingof pulp, which can be carried out in accordance with customaryprocesses. Also of interest is the use of metal complexes of compoundsof formula I as catalysts for reactions with peroxy compounds for thebleaching of waste printed paper.

It should be emphasised that the metal complexes of compounds of formulaI do not cause any appreciable damage to fibres and dyeings, for examplein the bleaching of textile material.

Processes for preventing the redeposition of migrating dyes in a washingliquor are usually carried out by adding to the washing liquor, whichcontains a peroxide-containing washing composition, one or more metalcomplexes of compounds of formula I in an amount of from 0.1 to 200 mg,preferably from 1 to 75 mg, especially from 3 to 50 mg, per litre ofwashing liquor. It will be understood that in such an application, aswell as in the other applications, the metal complexes of compounds offormula I can alternatively be formed in situ, the metal salt (e.g.manganese(II) salt, such as manganese(II) chloride) and the ligand beingadded in the desired molar ratios.

The present invention relates also to a washing, cleaning, disinfectingor bleaching composition, comprising

-   -   a) 0-50%, preferably 0-30%, of an anionic surfactant and/or of a        non-ionic surfactant,    -   b) 0-70%, preferably 0-50%, of a builder substance,    -   c) 1-99%, preferably 1-50%, of a peroxide or a peroxide-forming        substance, and    -   d) at least one metal complex of a compound of formula I in an        amount which, in the liquor, gives a concentration of 0.5-50        mg/litre of liquor, preferably 1-30 mg/litre of liquor, when        from 0.5 to 20 g/litre of the washing, cleaning, disinfecting or        bleaching composition are added to the liquor; the percentages        being in each case percentages by weight, based on the total        weight of the composition.

The compositions preferably contain from 0.005 to 2% of a metal complexcompound of formula 1, especially from 0.01 to 1% and preferably from0.05 to 1%.

When the compositions according to the invention comprise a component(a), the amount thereof is preferably 1-50%, especially 1-30%.

When the compositions according to the invention comprise a component(b), the amount thereof is preferably 1-70%, especially 1-50%. Specialpreference is given to an amount of from 5 to 50% and especially anamount of from 10 to 50%.

Corresponding washing, cleaning, disinfecting or bleaching processes areusually carried out by using an aqueous liquor comprising a peroxide andfrom 0.1 to 200 mg of one or more metal complexes of compounds offormula I per litre of liquor. The liquor preferably contains from 1 to30 mg of at least one metal complex of a compound of formula I per litreof liquor.

The composition according to the invention can be, for example, aperoxide-containing complete washing composition or a separate bleachingadditive. A bleaching additive is used for removing coloured stains ontextiles in a separate liquor before the clothes are washed with ableach-free washing composition. A bleaching additive can also be usedin a liquor together with a bleach-free washing composition.

The washing or cleaning composition according to the invention can be insolid or liquid form, for example in the form of a liquid, non-aqueouswashing composition, comprising not more than 5% by weight water,preferably comprising from 0 to 1% by weight water, and, as base, asuspension of a builder substance in a non-ionic surfactant, e.g. asdescribed in GB-A-2 158 454.

The washing or cleaning composition is preferably in the form of apowder or, especially, granules.

The latter can be prepared, for example, by first preparing an initialpowder by spray-drying an aqueous suspension containing all thecomponents listed above except for components (c) and (d), then addingthe dry components (c) and (d) and mixing everything together. It isalso possible to add component (d) to an aqueous suspension containingcomponents (a) and (b), then to carry out spray-drying and finally tomix component (c) with the dry mass.

It is also possible to start with an aqueous suspension that containscomponents (a) and (b), but none or only some of the non-ionicsurfactant. The suspension is spray-dried, then component (d) is mixedwith the non-ionic surfactant and added, and then component (c) is mixedin in the dry state.

It is also possible to mix all the components together in the dry state.

The anionic surfactant can be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture thereof. Preferred sulfates arethose having from 12 to 22 carbon atoms in the alkyl radical, optionallyin combination with alkyl ethoxysulfates in which the alkyl radical hasfrom 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15carbon atoms in the alkyl radical. The cation in the case of anionicsurfactants is preferably an alkali metal cation, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of formulaR—CO—N(R′¹)—CH₂COOM′¹ wherein R is alkyl or alkenyl having from 8 to 18carbon atoms in the alkyl or alkenyl radical, R′¹ is C₁-C₄alkyl and M′¹is an alkali metal.

The non-ionic surfactant can be, for example, a condensation product offrom 3 to 8 mol of ethylene oxide with 1 mol of a primary alcohol havingfrom 9 to 15 carbon atoms.

As builder substance there come into consideration, for example, alkalimetal phosphates, especially tripolyphosphates, carbonates or hydrogencarbonates, especially their sodium salts, silicates, aluminosilicates,polycarboxylates, polycarboxylic acids, organic phosphonates,aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds.

Especially suitable silicates are sodium salts of crystalline layeredsilicates of the formula NaHSi_(t)O_(2t+1).p H₂O or Na₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among the aluminosilicates, preference is given to those commerciallyavailable under the names Zeolite A, B, X and HS, and also to mixturescomprising two or more of those components.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred polycarboxylic acidsare nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylenediamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid anddiethylenetriaminepentamethylenephosphonic acid.

As peroxide component (c) there come into consideration, for example,the organic and inorganic peroxides known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 10 to 95° C.

The organic peroxides are, for example, mono- or poly-peroxides,especially organic peracids or salts thereof, such asphthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioicacid, diperoxynonanedioic acid, diperoxydecanedioic acid,diperoxyphthalic acid or salts thereof.

Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates. It will beunderstood that mixtures of inorganic and/or organic peroxides can alsobe used. The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability.

The peroxides are added to the composition preferably by mixing thecomponents, for example using a screw metering system and/or a fluidisedbed mixer.

The compositions may comprise, in addition to the combination accordingto the invention, one or more optical brighteners, for example from theclass bis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative, coumarin derivative or a pyrazolinederivative.

The compositions may also comprise suspending agents for dirt, e.g.sodium carboxymethylcellulose, pH regulators, e.g. alkali metal oralkaline earth metal silicates, foam regulators, e.g. soap, salts forregulating the spray-drying and the granulating properties, e.g. sodiumsulfate, perfumes and, optionally, antistatic agents and softeners,enzymes, such as amylase, bleaches, pigments and/or toning agents. Suchconstituents must especially be stable towards the bleach used.

In addition to the metal complexes of compounds of formula I it is alsopossible to use further transition metal salts or complexes known asbleach-activating active ingredients and/or conventional bleachactivators, that is to say compounds that, under perhydrolysisconditions, yield unsubstituted or substituted perbenzo- and/orperoxo-carboxylic acids having from 1 to 10 carbon atoms, especiallyfrom 2 to 4 carbon atoms. Suitable bleach activators include thecustomary bleach activators, mentioned at the beginning, that carry O-and/or N-acyl groups having the indicated number of carbon atoms and/orunsubstituted or substituted benzoyl groups. Preference is given topolyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),compounds of formula (4):

wherein R′₁ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R′₂ is linear or branched (C₇-C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA,acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-44 43 177. Nitrile compoundsthat form perimine acids with peroxides also come into consideration asbleach activators.

Further preferred additives to the compositions according to theinvention are polymers which, during the washing of textiles, preventstaining caused by dyes in the washing liquor that have been releasedfrom the textiles under the washing conditions. Such polymers arepreferably polyvinylpyrrolidones or polyvinylpyridine-N-oxides whch mayhave been modified by the incorporation of anionic or cationicsubstituents, especially those having a molecular weight in the range offrom 5000 to 60 000, more especially from 10 000 to 50 000. Suchpolymers are preferably used in an amount of from 0.05 to 5% by weight,especially from 0.2 to 1.7% by weight, based on the total weight of thewashing composition.

The invention relates also to solid preparations, especially granules,comprising:

-   -   A) from 1 to 99% by weight, preferably from 1 to 40% by weight,        e.g. from 1 to 30% by weight, of a metal complex of a compound        of formula I,    -   B) from 1 to 99% by weight, preferably from 10 to 99% by weight,        e.g. from 20 to 80% by weight, of a binder,    -   C) from 0 to 20% by weight, preferably from 1 to 20% by weight,        of an encapsulating material,    -   D) from 0 to 20% by weight of a further additive and    -   E) from 0 to 20% by weight of water.

As binder there come into consideration anionic dispersants, non-ionicdispersants, polymers and waxes that are water-soluble or dispersible oremulsifiable in water.

The anionic dispersants used are, for example, commercially availablewater-soluble anionic dispersants for dyes or pigments. The followingproducts, especially, come into consideration: condensation products ofaromatic sulfonic acids and formaldehyde, condensation products ofaromatic sulfonic acids with unsubstituted or chlorinated diphenylene ordiphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethanesulfonates, lignosulfonates or oxylignosulfonatesor heterocyclic polysulfonic acids.

Especially suitable anionic dispersants are condensation products ofnaphthalenesulfonic acids with formaldehyde, sodium salts of polymerisedorganic sulfonic acids, (mono-/di-)-alkylnaphthalenesulfonates,polyalkylated polynuclear arylsulfonates, sodium salts of polymerisedalkylbenzenesulfonic acids, lignosulfonates, oxylignosulfonates andcondensation products of naphthalenesulfonic acid with apolychloromethyldiphenyl.

Suitable non-ionic dispersants are especially compounds having a meltingpoint of, preferably, at least 35° C. that are emulsifiable, dispersibleor soluble in water, for example the following compounds:

-   1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl    alcohol;-   2. addition products of, preferably, from 2 to 80 mol of alkylene    oxide, especially ethylene oxide, wherein some of the ethylene oxide    units may have been replaced by substituted epoxides, such as    styrene oxide and/or propylene oxide, with higher unsaturated or    saturated monoalcohols, fatty acids, fatty amines or fatty amides    having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl    phenols, benzyl phenols or alkyl phenols, the alkyl radicals of    which have at least 4 carbon atoms;-   3. alkylene oxide condensation products, especially propylene oxide    condensation products (block polymers);-   4. ethylene oxide/propylene oxide adducts with diamines, especially    ethylenediamine;-   5. reaction products of a fatty acid having from 8 to 22 carbon    atoms and a primary or secondary amine having at least one    hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene    oxide addition products of such hydroxyalkyl-group-containing    reaction products;-   6. sorbitan esters, preferably with long-chain ester groups, or    ethoxylated sorbitan esters, such as polyoxyethylene sorbitan    monolaurate having from 4 to 10 ethylene oxide units or    polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene    oxide units;-   7. addition products of propylene oxide with a tri- to hexa-hydric    aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or    pentaerythritol;-   8. fatty alcohol polyglycol mixed ethers, especially addition    products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol    of propylene oxide with aliphatic monoalcohols having from 8 to 22    carbon atoms.

Especially suitable non-ionic dispersants are surfactants of formula (5)R′₁₁—O-(alkylene-O)_(n)-R′₁₂  (5)wherein

-   R′₁₁ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;-   R′₁₂ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at    least 6 carbon atoms; or benzyl;-   “alkylene” is an alkylene radical having from 2 to 4 carbon atoms    and-   n is a number from 1 to 60.

A substituent R′₁₁ or R′₁₂ in formula (5) is advantageously thehydrocarbyl radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbylradical may be straight-chain or branched. R′₁₁ and R′₁₂ are preferablyeach independently of the other an alkyl radical having from 9 to 14carbon atoms.

Aliphatic saturated monoalcohols that come into consideration includenatural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcoholor stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol,1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol,trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁oxo-alcohol,tridecyl alcohol, isotridecyl alcohol and linear primary alcohols(Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfolsare Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol(16-18). (“Alfol” is a registered trade mark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol,hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures oftwo or more components, e.g. mixtures of alkyl and/or alkenyl groupsthat are derived from soybean fatty acids, palm kernel fatty acids ortallow oils.

(Alkylene-O) chains are preferably divalent radicals of the formulae

Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl andpreferably cyclohexyl.

As non-ionic dispersants there come into consideration especiallysurfactants of formula (6)

wherein

-   R₁₃ is C₈-C₂₂alkyl;-   R₁₄ is hydrogen or C₁-C₄alkyl;-   Y₁, Y₂, Y₃ and Y₄ each independently of the others are hydrogen,    methyl or ethyl;-   m is a number from 0 to 8; and-   n is a number from 2 to 40.

Further important non-ionic dispersants correspond to formula (7)

wherein

-   R₁₅ is C₉-C₁₄alkyl;-   R₁₆ is C₁-C₄alkyl;-   Y₅, Y₆, Y₇ and Y₈ each independently of the others are hydrogen,    methyl or ethyl, one of the radicals Y₅, Y₆ and one of the radicals    Y₇, Y₈ always being hydrogen; and p and q each independently of the    other are an integer from 4 to 8.

The non-ionic dispersants of formulae (5) to (7) can be used in the formof mixtures. For example, as surfactant mixtures there come intoconsideration non-end-group-terminated fatty alcohol ethoxylates offormula (5), e.g. compounds of formula (5) wherein R₁₁ is C₈-C₂₂alkyl,R₁₂ is hydrogen and the alkylene-O chain is the radical —(CH₂—CH₂-O)—,and also end-group-terminated fatty alcohol ethoxylates of formula (7).

Examples of non-ionic dispersants of formulae (5), (6) and (7) includereaction products of a C₁₀-C₁₃fatty alcohol, e.g. a C₁₃oxo-alcohol, withfrom 3 to 10 mol of ethylene oxide, propylene oxide and/or butyleneoxide or the reaction product of one mol of a C₁₃fatty alcohol with 6mol of ethylene oxide and 1 mol of butylene oxide, it being possible forthe addition products each to be end-group-terminated with C₁-C₄alkyl,preferably methyl or butyl.

Such dispersants can be used singly or in the form of mixtures of two ormore dispersants.

Instead of, or in addition to, the anionic or non-ionic dispersant, thegranules according to the invention may comprise a water-soluble organicpolymer as binder. Such polymers may be used singly or in the form ofmixtures of two or more polymers.

Water-soluble polymers that come into consideration are, for example,polyethylene glycols, copolymers of ethylene oxide with propylene oxide,gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones,vinylpyrrolidones, vinyl acetates, polyvinylimidazoles,polyvinylpyridine-N-oxides, copolymers of vinylpyrrolidone withlong-chain α-olefins, copolymers of vinyl-pyrrolidone withvinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates),copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides,copolymers of vinyl-pyrrolidone/dimethylaminopropyl acrylamides,quaternised copolymers of vinylpyrrolidones and dimethylaminoethylmethacrylates, terpolymers ofvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamido-propyl-trimethylammonium chloride, terpolymers ofcaprolactam/vinylpyrrolidone/dimethyl-aminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose,polyvinyl alcohols, poly-vinyl acetate, hydrolysed polyvinyl acetate,copolymers of ethyl acrylate with methacrylate and methacrylic acid,copolymers of maleic acid with unsaturated hydrocarbons, and also mixedpolymerisation products of the mentioned polymers.

Of those organic polymers, special preference is given to polyethyleneglycols, carboxy-methylcellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, copolymers of ethyl acrylate with methacrylate andmethacrylic acid, and polymethacrylates.

Suitable water-emulsifiable or water-dispersible binders also includeparaffin waxes.

Encapsulating materials include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and polymethacrylates.

Further additives that come into consideration are, for example, wettingagents, dust removers, water-insoluble or water-soluble dyes orpigments, and also dissolution accelerators, optical brighteners andsequestering agents.

The preparation of the granules according to the invention is carriedout, for example, starting from a) a solution or suspension with asubsequent drying/shaping step or b) a suspension of the activeingredient in a melt with subsequent shaping and solidification.

In accordance with (a), first of all the anionic or non-ionic dispersantand/or the polymer and, if appropriate, the further additives aredissolved in water and stirred, if desired with heating, until ahomogeneous solution is obtained. The catalyst according to theinvention is then dissolved or suspended in the resulting aqueoussolution. The solids content of the solution should preferably be atleast 30% by weight, especially 40 to 50% by weight, based on the totalweight of the solution. The viscosity of the solution is preferably lessthan 200 mPas.

The aqueous solution so prepared, comprising the catalyst according tothe invention, is then subjected to a drying step in which all water,with the exception of a residual amount, is removed, solid particles(granules) being formed at the same time. Known methods are suitable forproducing the granules from the aqueous solution. In principle, bothcontinuous methods and discontinuous methods are suitable. Continuousmethods are preferred, especially spray-drying and fluidised bedgranulation processes.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is effected e.g. using unitary or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with an additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed integrated into the chamber(so-called fluid spray). The fine particles (<100 μm) obtained by aconventional spray-drying process may, if necessary after beingseparated from the exhaust gas flow, be fed as nuclei, without furthertreatment, directly into the atomising cone of the atomiser of thespray-dryer for the purpose of agglomeration with the liquid droplets ofthe active ingredient.

During the granulation step, the water can rapidly be removed from thesolutions comprising the metal complexes of compounds of formula Iaccording to the invention, binder and further additives. It isexpressly intended that agglomeration of the droplets forming in theatomising cone, or the agglomeration of droplets with solid particles,will take place.

If necessary, the granules formed in the spray-dryer are removed in acontinuous process, for example by a sieving operation. The fines andthe oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

A further preparation method according to (a) is a process in which thepolymer is mixed with water and then the catalyst according to theinvention is dissolved/suspended in the polymer solution, thus formingan aqueous phase, the catalyst according to the invention beinghomogeneously distributed in that phase. At the same time orsubsequently, the aqueous phase is dispersed in a water-immiscibleliquid in the presence of a dispersion stabiliser in order that a stabledispersion is formed. The water is then removed from the dispersion bydistillation, forming substantially dry particles. In those particles,the catalyst is homogeneously distributed in the polymer matrix.

The granules according to the invention are resistant to abrasion, lowin dust, pourable and readily meterable. They can be added directly to aformulation, such as a washing composition formulation, in the desiredconcentration of the catalyst according to the invention.

Where the coloured appearance of the granules in the washing compositionis to be suppressed, this can be achieved, for example, by embedding thegranules in a droplet of a whitish meltable substance (‘water-solublewax’) or by adding a white pigment (e.g. TiO₂) to the granuleformulation or, preferably, by encapsulating the granules in a meltconsisting, for example, of a water-soluble wax, as described in EP-A-0323 407, a white solid being added to the melt in order to reinforce themasking effect of the capsule.

In accordance with (b), the catalyst according to the invention is driedin a separate step prior to the melt-granulation and, if necessary,dry-ground in a mill so that all the solids particles are <50 μm insize. The drying is carried out in an apparatus customary for thepurpose, for example in a paddle dryer, vacuum cabinet or freeze-dryer.

The finely particulate catalyst is suspended in the molten carriermaterial and homogenised. The desired granules are produced from thesuspension in a shaping step with simultaneous solidification of themelt. The choice of a suitable melt-granulation process is made inaccordance with the desired size of granules. In principle, any processwhich can be used to produce granules in a particle size of from 0.1 to4 mm is suitable. Such processes are droplet processes (withsolidification on a cooling belt or during free fall in cold air),melt-prilling (cooling medium gas/liquid), and flake formation with asubsequent comminution step, the granulation apparatus being operatedcontinuously or discontinuously.

Where the coloured appearance of the granules prepared from a melt is tobe suppressed in the washing composition, in addition to the catalyst itis also possible to suspend in the melt white or coloured pigmentswhich, after solidification, impart the desired coloured appearance tothe granules (e.g. titanium dioxide).

If desired, the granules can be covered or encapsulated in anencapsulating material. Methods suitable for such an encapsulationinclude the customary methods and also the encapsulation of the granulesby a melt consisting e.g. of a water-soluble wax, as described, forexample, in EP-A-0 323 407, coacervation, complex coacervation andsurface polymerisation.

Encapsulating materials include e.g. water-soluble, water-dispersible orwater-emulsifiable polymers and waxes.

Further additives include e.g. wetting agents, dust-removers,water-insoluble or water-soluble dyes or pigments, and also dissolutionaccelerators, optical brighteners and sequestering agents.

Surprisingly, the metal complexes of compounds of formula I also exhibita markedly improved bleach-catalysing action on coloured stains on hardsurfaces. The addition of such metal complexes of compounds of formula Iin catalytic amounts to a dishwashing composition that comprises aperoxy compound and optionally TAED(N,N,N′,N′-tetraacetylethylenediamine) results in the substantialremoval of e.g. tea stains on china. This is the case even when hardwater is used, it being known that tea deposits are more difficult toremove in hard water than in soft water. The metal complexes ofcompounds of formula I are also very suitable for cleaning hard surfacesat low temperatures.

The use of metal complexes of compounds of formula I as catalysts forreactions with peroxy compounds in cleaning solutions for hard surfaces,especially for kitchen- and table-ware, is therefore of specialinterest.

The present invention relates also to cleaning compositions for hardsurfaces, especially cleaning compositions for table- and kitchen-wareand, among such compositions, preferably those for use in cleaningprocesses carried out by machine, which compositions comprise one of theabove-described metal complexes of compounds of formula I as bleachcatalyst. Suitable formulations for such cleaning compositions include,for example, the formulations mentioned above for the washingcompositions.

The metal complexes of compounds of formula I also have, together withperoxy compounds, excellent antibacterial action. The use of the metalcomplexes of compounds of formula I for killing bacteria or forprotecting against bacterial attack is therefore likewise of interest.

The metal complexes of compounds of formula I are also outstandinglysuitable for selective oxidation in the context of organic synthesis,especially the oxidation of organic molecules, e.g. of olefins to formepoxides. Such selective transformation reactions are requiredespecially in process chemistry. The invention accordingly relates alsoto the use of the metal complexes of compounds of formula I in selectiveoxidation reactions in the context of organic synthesis.

The present invention relates also to a method of catalysing oxidations,wherein at least one metal complex of a compound of formula I is addedto the oxidising agent.

Of special interest is a method of catalysing oxidations, wherein theoxidations relate to the bleaching of spots or stains on textilematerial or to the prevention of the redeposition of migrating dyes inthe context of a washing process, or to the cleaning of hard surfaces.

Likewise of interest is a method of catalysing oxidations, wherein theoxidising agent is a washing, cleaning, disinfecting or bleachingcomposition.

The following Examples serve to illustrate the invention but do notlimit the invention thereto. Parts and percentages relate to weight,unless otherwise indicated.

EXAMPLE 1 Preparation of an Iron Complex of Compound (101) withIron(III) Chloride

a) Preparation of 2-(2-hydroxyphenyl)-benzo-4H-[1,3]oxazin-4-one[compound (201)]

24.9 g (0.18 mol) of salicylic acid, 20.6 g (0.15 mol) of salicylamideand 1.5 ml of pyridine are heated at reflux in 30 ml of xylene. Withvigorous stirring, 23.7 ml (0.33 mol) of thionyl chloride are addeddropwise in the course of 4 hours. The product then begins tocrystallise. The reaction mixture is stirred for a further 30 minutesand then concentrated in a vacuum rotary evaporator. Crystallisation ofthe residue from methoxyethanol yields 19.8 g (55%) of compound (201) inthe form of fine yellow needles. ¹H NMR (DMSO-d₆): δ(ppm)=7.09 (m, 2H);7.62 (m, 2H); 7.78 (d, 1H); 7.94 (q, 1H); 8.07 (d, 1H); 8.20 (d, 1H);8.78 (OH).

b) Preparation of Compound (101)

0.8 g (4.25 mmol) of 4-hydrazinobenzosulfonic acid are suspended in 100ml of ethanol. 4.25 mmol of triethylamine and 1.0 g (4.18 mmol) of2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one [compound (201), Example1a] are added. The reaction mixture is boiled under reflux for 20 hours.After cooling to room temperature, 20 ml of 6N hydrochloric acid areadded to the reaction mixture which is then concentrated using a vacuumrotary evaporator until a precipitate is formed. A further 20 ml of 6Nhydrochloric acid are then added to the reaction mixture. Theprecipitate is filtered off, washed with a small amount of water anddried in vacuo in a drying cabinet. 1.10 g (61%) of compound (101) areobtained in the form of a bright yellow, hygroscopic powder. ¹H NMR(DMSO-d₆): δ(ppm)=6.91 (d, 1H); 6.95-7.01 (m, 2H); 7.05 (d, 1H);7.36-7.40 (dd, 2H); 7.46 (d, 2H); 7.51 (d, 1H); 7.72 (d, 2H); 8.02 (d,1H). C₂₀H₁₅N₃O₅S·H₂O (409.42). Analysis calculated: C, 56.02; H 4.24; N9.61%.

Analysis found: C, 56.20; H 4.01; N 9.83%.

c) Preparation of an Iron Complex of Compound (101) with Iron(III)Chloride

To a solution of 409 mg (1 mmol) of4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol)-1-yl-benzosulfonic acidmonohydrate [compound (101), prepared in accordance with Example 1b] in15 ml of methanol there is added an equimolar solution of anhydrousiron(III) chloride in methanol, the deep-violet monocomplex being formedspontaneously. The deep-violet solution is concentrated to 10 ml using avacuum rotary evaporator and filtered. A small amount of water andisopropanol is added to the filtrate; concentration is carried out usinga vacuum rotary evaporator and the residue is dried in vacuo in a dryingcabinet. Analysis calculated for FeC₂₀H₁₃N₃O₅S·CH₃OH·H₂O: C, 52.12; H3.58; N 8.29%. Analysis found: C, 52.26; H 3.49; N 8.31%.

EXAMPLE 2 Preparation of the Iron Complex of Compound (102) withIron(III) Chloride

a) Preparation of Compound (102)

1.75 g (11.50 mmol) of 4-hydrazinobenzoic acid are dissolved underreflux in 40 ml of ethanol. With continued heating, 2.50 g (10.45 mmol)of 2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one [compound (201),Example 1a] are added to the resulting clear solution. The reactionmixture is boiled under reflux for 3 hours, then cooled to roomtemperature and water is added until precipitation begins. The reactionmixture is then concentrated to half its volume using a vacuum rotaryevaporator and a further 40 ml of water are added. The precipitatedproduct is filtered off and dried in vacuo in a drying cabinet, yielding3.28 g (80%) of compound (102), bright yellow powder, which on beingleft to stand in the air absorbs moisture and at the same time becomeslighter in colour. ¹H NMR (DMSO-d₆): δ(ppm)=6.90 (d, 1H); 7.00 (dt, 2H);7.04 (d, 1H); 7.37 (dt, 2H); 7.55 (d, 1H); 7.58 (d, 2H); 8.02 (d, 2H);8.08 (d, 1H). C₂₁H₁₅N₃O₄·1.1H₂O. Analysis calculated: C64.11; H, 4.41; N10.69%. Analysis found: C 64.11; H, 4.60; N 10.44%.

b) Preparation of an Iron Complex of Compound (102) with Iron(III)Chloride

To a solution of 373 mg (1 mmol) of4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol)-1-yl-benzoic acid monohydrate[compound (102), prepared according to Example 2a] in 15 ml of methanolthere is added an equimolar solution of anhydrous iron(III) chloride inmethanol, the deep-violet monocomplex being formed spontaneously. Thedeep-violet solution is concentrated to 10 ml using a vacuum rotaryevaporator and filtered. A small amount of water and isopropanol isadded to the filtrate; concentration is carried out using a vacuumrotary evaporator and the residue is dried in vacuo in a drying cabinet.Analysis calculated for FeC₂₁H₁₃N₃O₄·4H₂O: C, 50.62; H 4.05; N 8.43%.Analysis found: C, 50.46; H 4.23; N 8.54%.

EXAMPLE 3 Preparation of the Iron Complex of Compound (103) withiron(III) Chloride

a) Preparation of Compound (103)

A solution of 1.45 g (10.3 mmol) of phenylhydrazine hydrochloride in 80ml of ethanol is heated briefly at reflux. After cooling to roomtemperature, 2.0 g (8.36 mmol) of2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one [compound (201), Example1a] are added. The reaction mixture is then boiled under reflux for afurther 2 hours. The clear, colourless reaction solution is cooled toroom temperature; 40 ml of 1 N hydrochloric acid are added and theprecipitated solid is filtered off and dried overnight in vacuo in adrying cabinet. Crystallisation of the residue from methanol yields 1.72g (63%) of compound (103). ¹H NMR (DMSO-d₆): δ(ppm)=6.89 (d, 1H); 6.94(t, 1H); 7.01 (t, 1H); 7.03 (d, 1H); 7.37 (t, 2H); 7.42-7.48 (m, 6H);7.85 (d, 1H); 9.88 (s, OH); 10.71 (s, OH). C₂₀H₁₅N₃O₂ (329.36). Analysiscalculated: N 12.76%. Analysis found: 12.67%.

b) Preparation of the Iron Complex of Compound (103) with Iron(III)Chloride

To a solution of 329 mg (1 mmol) of compound (103), prepared accordingto Example 3a, in 15 ml of ethanol there is added an equimolar solutionof anhydrous iron(III) chloride in ethanol, the deep-violet monocomplexbeing formed spontaneously. The deep-violet solution is concentrated to10 ml using a vacuum rotary evaporator and filtered. A small amount ofwater and isopropanol is added to the filtrate; concentration is carriedout using a vacuum rotary evaporator and the residue is dried in vacuoin a drying cabinet. Analysis calculated for FeC₂₀H₁₃N₃O₂Cl·C₂H₅OH·H₂O:C, 48.54; H 4.55; N 9.99%. Analysis found: C, 48.07; H 4.57; N 9.83%.

EXAMPLE 4 Preparation of an Iron Complex of Compound (103) withIron(III) Chloride

Saturated sodium ethanolate solution is added, with stirring, to asolution of 186 mg (1 mmol) of anhydrous iron(III) chloride and 660 mg(2 mmol) of compound (103), prepared according to Example 3a, in 20 mlethanol until a precipitate begins to form. The reaction mixture is leftto stand at 0° C. for 24 hours. The reddish-violet precipitate isfiltered off and dried in vacuo in a drying cabinet for 24 hours.Dark-red crystals are obtained. Na[Fe(C₂₀H₁₃N₃O₂)₂]·C₂H₅OH·2H₂O.Analysis calculated: C, 61.85; H 4.45; N 10.30%. Analysis found: C,62.49; H 4.15; N 10.0%.

EXAMPLE 5 Preparation of an Iron Complex of Compound (102) withIron(III) Chloride

A solution of 186 mg (1 mmol) of anhydrous iron(III) chloride and 740 mg(2 mmol) of compound (102), prepared according to Example 2a, in 20 mlmethanol is deprotonated with 0.1 M potassium hydroxide solution untilthe colour of the solution changes from violet to red. The resultingsolution is concentrated using a rotary evaporator and cooled to 8° C.After two days a red precipitate is formed, which is filtered off anddried in vacuo in a drying cabinet. A red powder is obtained.K₃[Fe(C₂₁H₁₃N₃O₄)₂]·2 CH₃OH·2H₂O. Analysis calculated: C, 52.12; H 3.58;N 8.29%. Analysis found: C, 52.26; H 3.49; N 8.31%.

EXAMPLE 6 Preparation of a Manganese Complex of Compound (103) withManganese(III) Acetate Dihydrate

660 mg (2 mmol) of compound (103), prepared according to Example 3a, in20 ml of methanol are added to a solution of 268 mg (1 mmol) ofmanganese(III) acetate dihydrate in 10 ml of methanol, a greenish-blackprecipitate being formed spontaneously. The dark-brown solution isconcentrated to 10 ml in a vacuum rotary evaporator and then filtered. Asmall amount of water and isopropanol is added to the filtrate;concentration is carried out using a vacuum rotary evaporator and theresidue is dried in vacuo in a drying cabinet. A brownish-black powderis obtained. ESI-MS [m/z] 709 [ML₂]; 710 [ML₂+H]⁺; 732 [ML₂+Na]⁺; 329(ligand).

EXAMPLE 7 Preparation of a Manganese Complex of Compound (102) withManganese(III) Acetate Dihydrate

To a solution of 427 mg (1 mmol) of compound (102), prepared accordingto Example 2a, in 15 ml of methanol there is added an equimolar solutionof manganese(III) acetate dihydrate in methanol, a brownish-blackprecipitate being formed spontaneously. The dark-brown solution isconcentrated to 10 ml using a vacuum rotary evaporator and thenfiltered. A small amount of water and isopropanol is added to thefiltrate; concentration is carried out using a vacuum rotary evaporator,followed by drying in vacuo in a drying cabinet. A brownish-black powderis obtained. ESI-MS [m/z] 797 [ML₂+H]⁺, 373 (ligand).

EXAMPLE 8 Preparation of Compound (104)

2.39 g (10 mmol) of 2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one[compound (201), Example 1a] are added, with intensive stirring, to asolution of 500 mg (10 mmol) of hydrazine hydrate in 50 ml of ethanol.The reaction mixture is boiled under reflux, then cooled andconcentrated to half using a vacuum rotary evaporator. 20 ml of 6Nhydrochloric acid are then added, with stirring, to the resultingreaction solution, which is then left to stand in a refrigerator for 24hours. The precipitated product is filtered off and dried in vacuo in adrying cabinet. 1.77 g (70%) of compound (104) are obtained in the formof a colourless powder. C₁₄H₁₁N₃O₂ (253.26). Analysis calculated: C,66.40; H 4.38; N 16.59%. Analysis found: C, 66.08; H 4.50; N 16.33%.

EXAMPLE 9 Preparation of Compound (105)

Analogously to Example 8, using 460 mg (10 mmol) of methylhydrazine and2.39 g (10 mmol) of 2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one[compound (201), Example 1a] there are obtained 1.87 g (70%) of compound(105) in the form of a colourless powder. C₁₅H₁₃N₃O₂ (267.29). Analysiscalculated: C, 67.41; H 4.90; N 15.72%. Analysis found: C, 67.80; H4.58; N 15.40%.

EXAMPLE 10 Preparation of Compound (106)

100 mg (0.418 mmol) of 2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one[compound (201), Example 1a] and 58.1 mg (0.836 mmol) of hydroxylaminehydrochloride are reacted in accordance with Y. I. Ryabukhin, L. N.Faleeva, V. G. Korobkova, Khim. Geterotsikl. Soedin 3 (1983) 406-410.The reaction is monitored by thin-layer chromatography (n-hexane/ethylacetate 1:1). 47 mg (44%) of compound (106), colourless, light-beigecrystals, are obtained. M.p. 171° C. [Lit. 167-168° C.]. ¹H NMR(DMSO-d₆) δ(ppm)=7.0-7.2 (m, 4H, aryl-H); 7.45 and 7.60 (m, each 2H,aryl-H).

EXAMPLE 11 Preparation of Compound (107)

a) 2-(2-Hydroxyphenyl)-7-methoxybenzo-[1,3]oxazin-4-one [compound (202)]

15.1 g (0.09 mol) of 2-hydroxy-4-methoxy-benzoic acid, 10.3 g (0.075mol) of salicylamide and 0.75 ml of pyridine are heated at reflux in 20ml of xylene. 12 ml (0.165 mol) of thionyl chloride are added dropwiseto the resulting clear solution in the course of 2.5 hours with vigorousstirring. The solution is maintained at reflux for 30 minutes, thencooled to room temperature and stirred for 10 hours to complete thereaction. The reaction solution is evaporated to dryness in vacuo.Crystallisation of the yellow crude product with phenoxyethanol yieldsthe desired product.

Yield: 3.34 g (17%), bright-yellow solid.

¹H NMR (DMSO-d₆) δ=3.87 (s, 3H), 6.63 (s, 1H), 6.7 (d, 1H), 7.59 (t,1H), 7.73 (d, 1H), 7.92 (t, 1H), 8.04 (d, 1H), 8.1 (d, 1H), 13.25 (s,1H, OH).

b) Preparation of Compound (107)

1 g (3.71 mmol) of 2-(2-hydroxyphenyl)-7-methoxybenzo[1,3]oxazin-4-one[compound (202), Example 11a] is added to a solution of 186 mg (3.71mmol) of hydrazine hydrate in 20 ml of ethanol. The bright-yellowsuspension is heated at reflux for 2 hours. After cooling to roomtemperature, the reaction mixture is concentrated to half its volume.The product then begins to crystallise. The crystals are filtered off,washed with a small amount of cold ethanol and dried in vacuo at 30° C.

Yield: 985 mg (94%), colourless crystals,

¹H NMR (DMSO-d₆): 3.35 (s, br, NH), 3.77 (s, 3H, OCH₃), 6.6 (m, 2H),6.95 (s, 1H), 7.00 (t, 1H), 7.35 (t, 1H), 8.0 and 8.92 (each d, 1H);11.0-12.0 (s, br, OH).

EXAMPLE 12 Preparation of Compound (108)

a) Preparation of 2-(2-hydroxyphenyl)-8-methoxy-benzo[1,3]oxazin-4-one[Compound (203)]

A reaction solution of 15.1 g (0.09 mol) of 2-hydroxy-3-methoxybenzoicacid, 10.28 g (0.075 mol) of salicylamide and 750 μl (0.0093 mol) ofpyridine in 60 ml of xylene is heated at reflux. Under reflux, 11.85 ml(0.164 mol) of thionyl chloride are added dropwise in the course of 4hours. The solution is allowed to cool to room temperature. The solutionis concentrated to half in vacuo and left to stand at 15° C. for 8hours. The precipitate formed is filtered off, washed with a smallamount of ethanol and recrystallised from methoxyethanol with theaddition of activated carbon. The end product is filtered and driedunder a high vacuum at 35° C. Yield: 4.8 g (20%), yellowish solid.

b) Preparation of Compound (108)

A solution of 108 μl (2.23 mmol) of hydrazine monohydrate in 12 ml ofethanol is reacted with 600 mg (2.23 mmol) of2-(2-hydroxyphenyl)-8-methoxy-benzo[1,3]oxazin-4-one [compound (203),Example 12a] and worked up as described in Example 11 b). 528 mg (84%)of colourless crystals are obtained.

¹H NMR (DMSO-d₆) δ=3.35 (s, br, NH); 3.83 (s, 3H, OCH₃); 6.9-7.1 (m,4H); 6.95 (s, 1H); 7.35 (t, 1H); 7.60 (d, 1H); 8.02 (d, 1H); 11.0-12.0(s, br, OH).

EXAMPLE 13 Preparation of Compound (109)

a) Preparation of2-(2-hydroxyphenyl)-8-isopropyl-benzo-[1,3]oxazin-4-one [Compound 204]

4.9 g (0.07 mol) of 2-hydroxy-3-isopropylbenzoic acid, 3.1 g (0.0225mol) of salicylamide and 225 μl (0.0028 mol) of pyridine are heated atreflux in 20 ml of xylene. 3.6 ml (0.05 mol) of thionyl chloride areadded dropwise to the resulting clear solution in the course of 4 hourswith vigorous stirring. The solution is maintained at reflux for 30minutes, then cooled to room temperature and stirred for 8 hours tocomplete the reaction. The reaction solution is concentrated to half invacuo and left to stand for one day at 8° C. A yellowish-green crystalslurry separates out. The crude product is filtered off and washed witha small amount of cold ethanol. Purification is carried out byrecrystallisation from methoxyethanol. Isolation is carried out byfiltration and subsequent drying at 35° C. under a high vacuum.

Yield: 2.3 g (31%), yellowish crystals.

¹H NMR (CDCl₃) δ=1.3 (d, 6H); 7.50 (m, 4H), 7.82 (t, 1H); 7.96 (d, 1H),8.22 (d, 1H).

b) Preparation of Compound (109)

626 mg (2.23 mmol) of2-(2-hydroxyphenyl)-8-isopropyl-benzo-[1,3]oxazin-4-one [compound (204),Example 13a] are slowly introduced into a solution of 108.2 μl (2.23mmol) of hydrazine monohydrate in 12 ml ethanol and the mixture isheated at reflux for 2.5 hours. After cooling to room temperature, thesolution is concentrated to half in vacuo. 7 ml (4 mol/l) ofhydrochloric acid are added dropwise, with stirring. The suspension iscooled at 8° C. for 24 hours, then diluted with 2 ml of cold ethanol.The precipitate is filtered off, washed with a small amount of coldethanol and dried under a high vacuum at 35° C.

Yield: 0.7 g (90%).

¹³C NMR (DMSO-d₆) δ=22.7 (CH₃), 26.7 (CH), 113.4 (quat. C), 116.9;119.6; 120.0; 124.4; 128.0; 128.8 (tert. CH), 136.1 (quat. C), 153.9 and156.1 (quat. C).

The compound is isolated in the form of the hydrochloride with onemolecule of water.

C₁₇H₁₇N₃O₂·H₂O·HCl (349.79) Analysis calculated: C, 58.37; H 5.76; N12.01%. Analysis found: C, 58.70; H 6.09; N 11.91%.

EXAMPLE 14 Preparation of Compound (110)

500 mg (2.09 mmol) of 2-(2-hydroxyphenyl)-benzo-4H-[1,3]-oxazin-4-one[compound (201), Example 1a] are added, with stirring, at roomtemperature to a solution of 261 mg (2.09 mmol) of tert-butyl hydrazinehydrochloride in 11 ml of ethanol. The resulting suspension is heated atreflux for 3 hours, a clear solution being formed. The solution isconcentrated to half, and 5 ml of 6N hydrochloric acid are added. Theprecipitate that forms is filtered off, washed with a small amount ofcold ethanol and dried at room temperature in a vacuum drying cabinet.

Yield: 192 mg (29%) of colourless crystals.

¹H NMR (DMSO-d₆) δ=1.5 (s, 6H), 2.55 (s, 2H), 4.40 (m, 1H), 7.05 (m,4H), 7.05 (m, 6H), 7.52 (m, 2H), 10.4 (s, br, 1H, OH), 11.4 (s, br, 1H).

EXAMPLE 15 Preparation of Compound (111)

a) Preparation of 2-(2-hydroxyphenyl)-7-chloro-benzo[1,3]oxazin-4-one[compound (205)]

225 μl (2.8 mmol) of pyridine are added dropwise to a reaction mixtureof 4.65 g (0.027 mol) of 4-chlorosalicylic acid and 3.1 g (0.0225 mol)of salicylamide. The mixture is heated at reflux, a clear solution beingformed. 3.55 ml (0.050 mol) of thionyl chloride are added dropwise inthe course of 3 hours at reflux. The solution is cooled to roomtemperature. 10 ml of xylene are added and stirring is carried out atroom temperature for 2 hours to complete the reaction. The reactionsolution is evaporated to dryness and suspended with 20 ml of ethanoland 225 ml of glacial acetic acid. The precipitate is filtered off andwashed with a small amount of ethanol. The crude product isrecrystallised from 2-methoxyethanol with the addition of activatedcarbon.

Yield: 2.8 g (38%).

¹H NMR (CDCl₃): δ=6.90 (m, 1H), 7.00 (m, 1H), 7.42 (m, 2H), 7.74 and7.94 (m, each 1H).

b) Preparation of Compound (111)

600 mg (2.18 mmol) of2-(2-hydroxyphenyl)-7-chloro-benzo-[1,3]oxazin-4-one [compound (205) ofExample 15 a] are introduced into a solution of 108 μl (2.18 mmol) ofhydrazine monohydrate in 12 ml of ethanol. The reaction solution isheated at reflux for 4 hours. After cooling to room temperature, theprecipitate is filtered off, washed with cold ethanol and dried at 35°C. under a high vacuum.

Yield: 601 mg (95%), colourless crystals,

¹H NMR (CDCl₃): δ=3.3-3.6 (br, 1H, NH), 7.05 (m, 4H), 7.38 (m, 1H), 8.06(m, 2H), 11.5-13.0 (s, br, 2H, OH).

EXAMPLE 16 Preparation of Compound (112)

a) 2-(2-Hydroxyphenyl)-6-chloro-benzo[1,3]oxazin-4-one [compound (206)]

A reaction solution of 4.65 g (0.027 mol) of 5-chlorosalicylic acid and3.1 g (0.0225 mol) of salicylamide is reacted with 225 μl (0.028 mol) ofpyridine and 3.55 ml (0.050 mol) of thionyl chloride, worked up andrecrystallised as described in Example 15 a).

Yield: 2.3 g (32%), colourless solid.

¹H NMR. (CDCl₃): δ=6.97 (m, 1H), 7.43 (m, 2H); 7.7; 8.0 and 8.1 (m, 1H).

b) Preparation of Compound (112)

A reaction solution of 108 μl (2.18 mmol) of hydrazine monohydrate, 600mg (2.18 mmol) of 2-(2-hydroxyphenyl)-6-chloro-benzo[1,3]oxazin-4-one[compound (206) of Example 16 a] is reacted and worked up as describedin Example 15 b). Yield: 541 mg (86%), colourless solid.

¹H NMR (DMSO-d₆): δ=3.33 (br, 1H, NH), 7.04 (m, 3H), 7.37 (m, 2H), 8.02(m, 2H), 10.6-12.0 (s, br, 2H, OH).

EXAMPLE 17A Prevention of the Deposition of Dyes on Cotton During theWashing Process

For testing the activity of the catalysts, the DTI activity isdetermined. The DTI (Dye Transfer Inhibition) activity a is defined asthe following percentage.a=([Y(E)−Y(A)]/[Y(W)−Y(A)])*100where Y(W), Y(A) and Y(E) are the CIE lightness values of the whitematerial, of the material treated without the addition of catalyst andof the material treated with the addition of catalyst, in that order.a=0 denotes a completely useless product, the addition of which to thewashing liquor allows dye transfer to take place freely, whereas a=100%corresponds to a perfect catalyst which totally prevents the staining ofthe white material.

The following test system is used to obtain the test data: 7.5 g ofwhite cotton fabric are treated in 80 ml of washing liquor. The liquorcontains the standard washing composition ECE phosphate-free (456 IEC)EMPA, Switzerland, in a concentration of 7.5 g/l, 8.6 mmol/l H₂O₂ and asolution of the test dye. The washing operation is carried out in abeaker in a LINITEST apparatus for 30 minutes at 40° C. The catalystsare used in the standard manner in the concentrations indicated. As arepresentative commercial dye, the dye F4 (Reactive Blue 238) is used.The reflection spectra of the samples are measured using a Spectraflash200 and converted into lightness values (D65/10) in accordance with astandard CIE procedure. The manganese complexes according to theinvention are prepared from the corresponding ligands in situimmediately before the screening, a solution of 10 mmol of manganese(II)chloride in water being added to a solution of 10 mmol of ligand inmethanol/water.

Table 1 below shows the results obtained with the manganese complexesobtained in accordance with an in situ process. Table 1 gives DTIeffects a as a function of catalyst concentration, under use conditionsas described above. The activity is measured at catalyst concentrationsof 5 μM, 20 μM and 50 μM. In addition, measurements are made at aconcentration of 20 μM in the presence of Dequest® 2041[ethylenediaminetetramethylenephosphoric acid of formula P1]. TABLE 1(P1)

Manganese complex of a(%) a(%) a (%) + Ex- ligand from a (%) 20 μM 50 μMDequest amples Example No. 5 μM (F4) (F4) (F4) 20 μM (F4) 17a 1b 85 9797 96 17b 2a 73 89 97 98 17c  8 82 97 92 95 17d 11 67 17e 12 82 17f 1384 17g 14 60

The results in Table 1 show that the manganese complexes, obtained inaccordance with an in situ process and starting from the ligandsaccording to Examples 1b, 2a, 8, 11, 12, 13 and 14, are very effectivein preventing the redeposition of the dye on cotton.

EXAMPLE 18 Prevention of the Deposition of Dyes on Cotton During theWashing Process

The following test system is used to obtain the test data:

7.5 g of white cotton fabric are treated in 80 ml of washing liquor(liquor ratio 1:10). The liquor contains the liquid detergent in aconcentration of 4.0 g/l, 8.6 mmol/l H₂O₂ and a solution of the testdye. Two liquid detergents are used with the following composition:component Det. A Det. B Marlon A375 14 14 Edenor K12-18 12 3 Neodol45-7E 20 11 Triethanolamine 5 2 Ethanolamine 5 4 Isopropanol 1 4Propylene glycol 11 4 Citric acid 50% 2 4 Water 30 54 pH 9.4 9.8

The washing operation is carried out in a beaker in a LINITEST apparatusfor 30 minutes at 40° C. The catalyst is used in the standard manner inthe concentrations indicated. As a representative commercial dye, thedye F4 (Reactive Blue 238) is used. The reflection spectra of thesamples are measured using a Spectraflash 200 and converted intolightness values (D65/10) in accordance with a standard CIE procedure.The manganese complexes are prepared following the in situ proceduredescribed in Example 17 with methanol as solvent.

Table 2 below shows the results obtained with the manganese complex ofthe ligand described in Example 8.

Table 2 gives DTI effects a as a function of catalyst concentration,under use conditions as described above. The activity is measured atcatalyst concentrations of 20 mM and 50 mM with liquid detergents A andB. TABLE 2 Manganese complex of ligand from a (%) a (%) Examples ExampleNo. 20 mM (F4) 50 mM (F4) Detergent 18a 8 65 77 Det. A 18b 8 68 79 Det.B

The results in Table 2 show that the manganese complexes, obtained inaccordance with an in situ process and starting from the ligandsaccording to Example 8 are very effective in preventing the redepositionof the dye on cotton.

EXAMPLE 19 Bleaching of Tea Stains on Cotton Fabric

The bleaching action of the manganese complex of the ligand4-(3,5-bis(2-hydroxyphenyl)-1,2,4-triazol)-1-yl-benzosulfonic acidmonohydrate of Example 1b, which is prepared in situ with manganese(III)acetate, is tested under the following conditions: a cloth (4 cm×9 cm)made of cotton fabric stained with commercially available tea (BC-01,CFT) is treated in a bleaching liquor. The liquor contains 100 ml ofwater (2.2 ° dH), 0.4577 g of sodium percarbonate and the catalyst oractivator in the concentration given in Table 3. The washing operationis carried out in a steel beaker in a LINITEST apparatus for 10 minutesat 30° C. For evaluating the bleaching results, the increase inlightness, DY (difference in lightness according to CIE), of the stainsbrought about by the treatment is used. The results are summarised inTable 3. TABLE 3 Manganese complex of ligand Examples of Example No. 1bDY 19a^(a)) — 7.8 19b^(a)) 200 mg TAED 9.6 19c^(b))  5 mg 10.9 19d^(b)) 25 mg 13.9^(a))Comparison Example^(b))Example according to the invention

The results show that the catalyst according to the invention (in situmanganese complex of the ligand of Example 1b) significantly increasesthe bleaching action of sodium percarbonate under these conditions.Under these conditions, a significantly better bleaching action isobtained with this catalyst than with the conventional bleach activatorTAED [tetraacetylethylenediamine] of formula B1

even when the latter is present in a substantially higher concentration.

1. A method of catalysing an oxidation reaction, which comprises addingto a reaction mixture comprising an oxidizable substrate an oxidisingagent and at least one metal complex of a compound of the formula I

wherein X is oxygen or

R₁ and R₂ each independently of the other are halogen, hydroxy, cyano,nitro,

—SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted C₁-C₈alkoxy;chloro-substituted C₁-C₈alkyl; chloro-substituted C₁-C₈alkoxy;C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino, C₁-C₈acylamino,di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₀-C₈alkoxy or C₁-C₈alkanoyl, R₃ ishydrogen, C₁-C₁₂alkyl, phenyl or

R₄ is —OR₁₀, —NH₂, —NHR₁₁,

R₅ is —OR₁₀, C₁-C₈alkyl or —NH₂, R₆ is hydrogen, C₁-C₈alkyl orC₇-C₉phenylalkyl, R₇ is hydrogen, C₁-C₈alkyl or C₇-C₉phenylalkyl, R₈ isunsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene, R₉ is halogen,hydroxy, cyano, nitro,

—SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted C₁-C₈alkoxy;chloro-substituted C₁-C₈alkyl; chloro-substituted C₁-C₈alkoxy;C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino, C₁-C₈acylamino,di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl, R₁₀ ishydrogen, sodium or potassium, R₁₁ and R₁₂ each independently of theother are C₁-C₈alkyl, Y⁻ is a monovalent anion, m is 1 or 2, and n is 0,1, 2 or
 3. 2. A method according to claim 1, wherein the metal is iron,manganese, titanium, cobalt, nickel or copper.
 3. A method according toclaim 1, wherein X is oxygen or

R₁ and R₂ each independently of the other are chlorine, bromine,hydroxy, cyano, nitro,

—SO₂R₅, trifluoromethyl, trifluoromethoxy; chloromethyl,trichloromethyl, trichloromethoxy, benzyloxy, amino, C₁-C₄alkylamino,C₁-C₄acylamino, di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₄alkyl, C₁-C₄alkoxy or C₂-C₄alkanoyl, R₃ ishydrogen, C₁-C₈alkyl, phenyl or

R₄ is —OR₁₀, —NH₂, —NHR₁₁,

R₅ is —OR₁₀, C₁-C₄alkyl or —NH₂, R₆ is hydrogen, C₁-C₄alkyl or benzyl,R₇ is hydrogen, C₁-C₄alkyl or benzyl, R₈ is C₂-C₈alkylene, R₉ isfluorine, chlorine, bromine, hydroxy, cyano, nitro,

—SO₂R₅, trifluoromethyl; trifluoromethoxy; chloromethyl,trichloromethyl, chloromethoxy, benzyloxy, amino, C₁-C₄alkylamino,C₁-C₄acylamino, di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₄alkyl, C₁-C₄alkoxy or C₂-C₄alkanoyl, R₁₀ ishydrogen, sodium or potassium, R₁₁, and R₁₂ each independently of theother are C₀-C₄alkyl, Y⁻ is halide, nitrate or carboxylate, m is 1 or 2,and n is 0, 1 or
 2. 4. A method according to claim 1, wherein X isoxygen or

R¹ and R₂ each independently of the other are chlorine, hydroxy, cyano,

—SO₂R₅, C₁-C₄acylamino, di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₄alkyl, methoxy, chloromethyl or C₂-C₄alkanoyl,R₃ is hydrogen, C₁-C₈alkyl, phenyl or

R₄ is —OR₁₀, —NH₂, —NHR₁₁ or

R₅ is —OR₁₀, methyl or —NH₂, R₆ and R₇ each independently of the otherare hydrogen, C₁-C₄alkyl or benzyl, R₉ is chlorine, hydroxy, cyano,nitro,

—SO₂R₅ or methoxy, R₁₀ is hydrogen, sodium or potassium, R₁₁ and R₁₂each independently of the other are C₁-C₄alkyl, Y⁻ is chloride orcarboxylate, m is 1, and n is 0 or
 1. 5. A method according to claim 1,wherein the metal is iron or manganese, X is oxygen or

R₃ is hydrogen, C₁-C₄alkyl, phenyl or

R₄ and R₅ are —OR₁₀, R₉ is

or —SO₂R₅, R₁₀ is hydrogen, m is 1, and n is
 0. 6. A method according toclaim 1, wherein a metal complex of a compound of formula I is used in awashing, cleaning, disinfecting or bleaching composition.
 7. A methodaccording to claim 1, wherein a metal complex of a compound of formula Iis formed from a compound of formula I according to claim 1 and a metalsalt in situ in a washing, cleaning, disinfecting or bleachingcomposition.
 8. A method according to claim 1, wherein a metal complexof a compound of formula I is used together with a peroxy compound forthe bleaching of spots or stains on textile material or for theprevention of redeposition of migrating dyes in the context of a washingprocess, or for the cleaning of hard surfaces.
 9. A method according toclaim 1, wherein a metal complex of a compound of formula I is used ascatalyst for reactions with peroxy compounds for bleaching in apaper-making process.
 10. A method according to claim 1, wherein a metalcomplex of a compound of formula I is used as catalyst for selectiveoxidations in an organic synthesis.
 11. A metal complex of a compound offormula I

wherein X is oxygen or

R₁ and R₂ each independently of the other are halogen, hydroxy, cyano,nitro,

—SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted C₁-C₈alkoxy;chloro-substituted C₁-C₈alkyl; chloro-substituted C₁-C₈alkoxy;C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino, C₁-C₈acylamino,di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl, R₃ ishydrogen, C₁-C₁₂alkyl, phenyl or

R₄ is —OR₁₀, —NH₂, —NHR₁₁,

R₅ is —OR₁₀, C₁-C₈alkyl or —NH₂, R₆ is hydrogen, C₁-C₈alkyl orC₇-C₉phenylalkyl, R₇ is hydrogen, C₁-C₈alkyl or C₇-C₉phenylalkyl, R₈ isunsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene, R₉ is halogen,hydroxy, cyano, nitro,

—SO₂R₅, fluoro-substituted C₁-C₈alkyl; fluoro-substituted C₁-C₈alkoxy;chloro-substituted C₁-C₈alkyl; chloro-substituted C₁-C₈alkoxy;C₇-C₉phenylalkoxy, amino, C₁-C₈alkylamino, C₁-C₈acylamino,di(C₁-C₄alkyl)amino,

di(C₁-C₄acyl)amino, C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkanoyl, R₁₀ ishydrogen, sodium or potassium, R₁₁ and R₁₂ each independently of theother are C₁-C₈alkyl, Y⁻ is a monovalent anion, m is 1 or 2, and n is 0,1, 2 or
 3. 12. A metal complex of a compound of formula I as describedin claim 1 wherein the metal is iron or manganese, X is oxygen or

and R₃ is hydrogen, C₁-C₄alkyl, phenyl or

R₄ and R₅ are —OR₁₀, R₉ is

or —SO₂R₅, R₁₀ is hydrogen, m is 1, and n is
 0. 13. A washing, cleaning,disinfecting or bleaching composition, comprising a) 0-50% of an anionicsurfactant and/or of a non-ionic surfactant, b) 0-70% of a buildersubstance, c) 1-99% of a peroxide or a peroxide-forming substance, andd) at least one metal complex of a compound of formula I as described inclaim 1 in an amount which, in the liquor, gives a concentration of0.5-50 mg/litre of liquor when from 0.5 to 20 g/litre of the washing,cleaning, disinfecting or bleaching composition are added to the liquor;the percentages being in each case percentages by weight, based on thetotal weight of the composition.
 14. A solid preparation, comprising A)from 1 to 99% by weight of a metal complex of a compound of formula I asdescribed in claim 1, B) from 1 to 99% by weight of a binder, C) from 0to 20% by weight of an encapsulating material, D) from 0 to 20% byweight of a further additive and E) from 0 to 20% by weight of water.15. A solid preparation according to claim 14, which is in the form ofgranules.
 16. A method according to claim 1, wherein at least one metalcomplex of a compound of formula I is added to the oxidising agent. 17.A method according to claim 16, wherein the oxidations relate to thebleaching of spots or stains on textile material or to the prevention ofthe redeposition of migrating dyes in the context of a washing process,or to the cleaning of hard surfaces.
 18. Method according to claim 16,wherein the oxidising agent is a washing, cleaning, disinfecting orbleaching composition.